Mixtures of optically active cyclohexenone oxime ethers, their preparation, intermediates for this purpose and their use as herbicides

ABSTRACT

Mixtures of optically active cyclohexenone oxime ethers having R- and S-configuration in the oxime ether moiety of the formula I ##STR1## (R 1  =C 1  -C 6  -alkyl; ##STR2## X=C 1-C   4  -alkyl, C 1  -C 4  -haloalkyl; m=0-3 or 1-4 where all X&#39;s are halogen; 
     n=0-3 or 1-5 where all X&#39;s are halogen; 
     R 2  =C 1  -C 4  -alkoxy-C 1  -C 6  -alkyl, C 1  -C 4  -alkylthio-C 1  -C 6  -alkyl, substituted or unsubstituted C 3  -C 7  -cycloalkyl, substituted or unsubstituted C 5  -C 7  -cycloalkenyl, substituted or unsubstituted 5-membered saturated heterocyclic structure, substituted or unsubstituted 6- or 7-membered heterocyclic structure, substituted or unsubstituted 5-membered heteroaromatic structure, substituted or unsubstituted phenyl or pyridyl) 
     and their agriculturally useful salts and esters with C 1  -C 10  -carboxylic acids and inorganic acids.

This application is a 371 of PCT/EP93/00210, filed Jan. 30, 1993.

The present invention relates to novel mixtures of optically activecyclohexenone oxime ethers having the R- and S-configuration in theoxime ether moiety and of the general formula I ##STR3## where

R¹ is C₁ -C₆ -alkyl;

Z is one of the following groups: ##STR4##

X is halogen or C₁ -C₄ -haloalkyl;

m is from 0 to 3, or from 1 to 4 where all X are halogen;

n is from 0 to 3, or from 1 to 5 where all X are halogen;

R² is C₁ -C₄ -alkoxy-C₁ -C₆ -alkyl or C₁ -C₄ -alkylthio-C₁ -C₆ -alkyl;

C₃ -C₇ -cycloalkyl or C₅ -C₇ -cycloalkenyl, where these groups may, ifdesired, carry from one to three substituents selected from the groupconsisting of C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, C₁ -C₄ -alkylthio, C₁ -C₄-haloalkyl, hydroxyl and halogen;

a 5-membered saturated heterocyclic structure which contains one or twooxygen and/or sulfur atoms as hetero atoms and may, if desired,furthermore carry from one to three substituents selected from the groupconsisting of C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, C₁ -C₄ -alkylthio and C₁-C₄ -haloalkyl;

a 6-membered or 7-membered saturated or mono- or di-unsaturatedheterocyclic structure which contains one or two oxygen or sulfur atomsor one oxygen and one sulfur atom as hetero atoms and may, if desired,furthermore carry from one to three substituents selected from the groupconsisting of hydroxyl, halogen, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, C₁ -C₄-alkylthio and C₁ -C₄ -haloalkyl;

a 5-membered heteroaromatic structure containing from one to threehetero atoms selected from the group consisting of one or two nitrogenatoms and one oxygen or sulfur atom, where the heteroaromatic structuremay, if desired, furthermore carry from one to three substituentsselected from the group consisting of halogen, cyano, C₁ -C₄ -alkyl, C₁-C₄ -alkoxy, C₁ -C₄ -alkylthio, C₁ -C₄ -haloalkyl, C₂ -C₆ -alkenyl, C₂-C₆ -alkenyloxy and C₁ -C₄ -alkoxy-C₁ -C₄ -alkyl; phenyl or pyridyl,where these aromatic structures may, if desired, furthermore carry fromone to three substituents selected from the group consisting of halogen,nitro, cyano, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, C₁ -C₄ -alkylthio, C₁ -C₄-haloalkyl, C₃ -C₆ -alkenyloxy, C₃ -C₆ -alkynyloxy and an amino group--NR^(a) R^(b), where

R^(a) is hydrogen, C₁ -C₄ -alkyl, C₃ -C₆ -alkenyl or C₃ -C₆ -alkynyl,

R^(b) is hydrogen, C₁ -C₄ -alkyl, C₃ -C₆ -alkenyl, C₃ -C₆ -alkynyl, C₁-C₆ -acyl or benzoyl which, if desired, in turn may furthermore carryfrom one to three radicals selected from the group consisting of nitro,cyano, halogen, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, C₁ -C₄ -alkylthio and C₁-C₄ -haloalkyl, and the agriculturally useful salts and esters of thecompounds I with C₁ -C₁₀ -carboxylic acids and inorganic acids.

The present invention furthermore relates to a process for thepreparation of these compounds, their use as herbicides, and herbicideswhich contain these mixtures.

The present invention also relates to novel mixtures of optically activehydroxylamines having the R- and S-configuration of the formula III##STR5## where

Z is one of the following groups: ##STR6## where

X is halogen or C₁ -C₄ -haloalkyl,

m is from 0 to 3, or from 1 to 4 where all X are halogen, and

n is from 0 to 3, or from 1 to 5 where all X are halogen.

The literature discloses herbicidal cyclohexanediones of the formula I'##STR7## where R^(c), R^(d) and R^(e) have, inter alia, the followingmeanings:

U.S. Pat. No. 4,440,566 (R^(c) is ethyl or propyl, R^(d) is benzyl andR^(e) is 2-ethylthiopropyl);

EP-A 238 021 and EP-A 125 094 (R^(c) is ethyl or propyl, R^(d) is benzylor but-2-enyl and R^(e) is a substituted 5-membered hetaryl radical);

EP-A 80 301 (R^(c) is ethyl or propyl, R^(d) is benzyl or but-2-enyl andR^(e) is substituted phenyl);

DE-A 38 38 309 (R^(c) is ethyl or propyl, R^(d) is a substituted4-phenylbutylene or 4-phenylbutenylene radical and R^(e) is asubstituted 5-membered to 7-membered heterocyclic structure);

EP-A 456 112 (R^(c) is ethyl or propyl, R^(d) is a substituted3-phenoxypropylene or 2-phenoxyethylene radical and R^(e) is asubstituted 5-membered to 7-membered heterocyclic structure).

However, the herbicidal properties of these compounds, particularly withregard to their selectivity toward grass weeds in gramineous crops, maybe satisfactory only to a limited extent.

Hence, it was an object of the present invention to provide novelmixtures of cyclohexenone oxime ethers having improved selectivitytowards grass weeds in gramineous crops, such as rice and corn.

We have found that this object is achieved by the mixtures of opticallyactive cyclohexenone oxime ethers I, defined at the outset. We have alsofound herbicides which contain these mixtures.

The mixtures of optically active cyclohexenone oxime ethers I areobtainable by various methods, preferably in a conventional manner fromknown cyclohexenones of the formula II (DE-A 38 38 309, EP-A 243 313 andEP-A 456 112) and the corresponding mixtures of optically activehydroxylamines having the R- and S-configuration of the formula III (cf.EP-A 169 521): ##STR8##

A suitable salt of the hydroxylamines III is preferably used, inparticular the hydrochloride thereof, and the reaction is carried out inthe heterogeneous phase in an inert solvent, for example in dimethylsulfoxide, an alcohol, such as methanol, ethanol and isopropanol, anaromatic hydrocarbon, such as benzene and toluene, a chlorohydrocarbon,such as chloroform and 1,2-dichloroethane, an aliphatic hydrocarbon,such as hexane and cyclohexane, an ester, such as ethyl acetate, or anether, such as diethyl ether, dioxane and tetrahydrofuran.

The reaction is carried out in the presence of a base, from about 0.5 to2 mol equivalents, based on the ammonium compound, of a base usuallybeing sufficient,

Examples of suitable bases are carbonates, hydrocarbonates, acetates,alcoholates or oxides of alkali or alkaline earth metals, in particularsodium hydroxide, potassium hydroxide, magnesium oxide or calcium oxide.Organic bases, such as pyridine and tertiary amines, eg. triethylamine,are also suitable.

The reaction is preferably carried out in methanol, using sodiumbicarbonate as the base.

In a variant of the process, the reaction is carried out in the absenceof a base, using the free hydroxylamine bases III, for example in theform of an aqueous solution; depending on the solvent used for thecompound II, a one- or two-phase reaction mixture is obtained.

Examples of suitable solvents for this variant are alcohols, such asmethanol, ethanol, isopropanol and cyclohexanol, aliphatic and aromatichydrocarbons and chlorohydrocarbons, such as hexane, cyclohexane,methylene chloride, toluene and 1,2-dichloroethane, esters, such asethyl acetate, nitriles, such as acetonitrile, and cyclic ethers, suchas dioxane and tetrahydrofuran.

The cyclohexenone II and the mixture of optically active hydroxylaminesIII or the salts thereof are expediently used in a roughlystoichiometric ratio, with in some cases an excess of up to about 10 mol% of one or the other component may also be advantageous.

The reaction temperatures in general are from 0° C. to the boiling pointof the reaction mixture, preferably from 20° to 80° C.

The reaction is complete after a few hours. The product can be isolatedin a conventional manner, for example by evaporating down the mixture,partitioning the residue between methylene chloride and water anddistilling off the solvent under reduced pressure.

There is no need to ensure particular conditions with regard to thepressure; in general, the reaction is therefore carried out atatmospheric pressure or under the autogenous pressure of the particulardiluent.

Owing to their acidic character, the optically active cyclohexenoneoxime ethers I can form salts of alkali or alkaline earth metalcompounds and enol esters.

Alkali metal salts of the compounds I can be obtained by treating the3-hydroxycyclohexenone compounds with sodium hydroxide, potassiumhydroxide or a sodium or potassium alcoholate in aqueous solution or inan organic solvent, such as methanol, ethanol, acetone and toluene.

Other metal salts, such as manganese, copper, zinc, iron, calcium,magnesium and barium salts, can be prepared from the sodium salts in aconventional manner, as can ammonium and phosphonium salts by means ofammonia or phosphonium, sulfonium or sulfoxonium hydroxides.

The esters of the compounds I are likewise obtainable in a conventionalmanner (cf. for example Organikum, VEB Deutscher Verlag derWissenschaften, 17th Edition, Berlin 1988, pages 405-408).

The novel mixtures of optically active hydroxylamines III can beprepared via a number of known process steps, starting from knownintermediates: ##STR9##

L=a leaving group, eg. halogen, such as chlorine, bromine or iodine, orCH₃ SO₂ --O--.

The optically active alkylating agent V (Z. Naturforsch. 37 B (1982),912; DE-A 26 11 695) or, if desired, the optically active carbinol IV(Z. Naturforsch. 37 B (1982), 912; DE-A 26 11 695; U.S. Pat. No.4,491,468; EP-A 003 877; DE-A 25 43 179; DE-A 26 49 706; DE-A 24 15 867)is preferably coupled by the Mitsunobu method (Synthesis 1, 1981; J.Med. Chem. 33 (1990), 187) with a cyclic hydroximide VI, and theresulting protected hydroxylamine derivative VII is cleaved, for examplewith 2-aminoethanol, to give the free hydroxylamine III.

In the cyclic hydroximides VI, D is, for example, C₂ or C₃ -alkylene, C₂-alkenylene or a 5-membered or 6-membered ring which may have a nitrogenatom and may be saturated, partially unsaturated or aromatic, forexample phenylene, pyridylene, cyclopentylene, cyclohexylene orcyclohexenylene.

Examples of suitable substances are the following: ##STR10##

The reaction of the optically active alkylating agent V with thehydroximide VI is advantageously carried out in the presence of a base.All bases which are capable of deprotonating the hydroximides VI withoutattacking the imide system are in principle suitable. These are inparticular the nonnucleophilic bases.

Examples are mineral bases, such as alkali metal and alkaline earthmetal carbonates, and alkali metal and alkaline earth metalbicarbonates, and organic bases, such as aliphatic, cycloaliphatic andaromatic tertiary amines. However, mixtures of these bases may also beused.

Examples of individual compounds are the following bases: sodiumcarbonate, potassium carbonate, magnesium carbonate, calcium carbonate,barium carbonate, the bicarbonates of these metals, trimethylamine,triethylamine, tributylamine, ethyldiisopropylamine,N,N-dimethylaniline, 4-(N,N-dimethylamino)-pyridine, diazabicyclooctane,diazabicycloundecane, N-methylpiperidine, 1,4-dimethylpiperazine,pyridine, quinoline, bipyridine and phenanthroline. The economical basessodium carbonate and potassium carbonate are preferred.

The base is added in general in an equivalent amount to an excess of 5equivalents, based on the hydroximide. A greater excess is possible butgenerally has no additional advantages. It is also possible to use asmall amount of base. However, from 1 to 3, in particular from 1 to 2,equivalents, based on the hydroximide VI, of a base are preferably used.

The use of nucleophilic bases, for example alkali metal and alkalineearth metal hydroxides, in particular sodium hydroxide and potassiumhydroxide, is also possible. In this case, it is also advantageous touse the base in equivalent amounts, based on the hydroximide VI, inorder to avoid a nucleophilic attack by the hydroxyl ions on thecarbonyl function of the imide group.

The optically active alkylating agents V are expediently reacted withthe hydroximides VI in a solvent which is inert under the reactionconditions. Examples of advantageous solvents are polar, aproticsolvents, such as dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, sulfolane and cyclic ureas. The amount of solvent is ingeneral not critical.

The reaction of the optically active alkylating agent V with thehydroximide VI can also be carried out using phase transfer catalysis.In this case, solvents which form two phases with water are used,preferably chlorohydrocarbons. Suitable phase transfer catalysts are thequaternary ammonium and phosphonium salts, polyethylene glycols,polyethylene glycol ethers and crown ethers usually used for suchpurposes, as described, for example, by Dehmlow et al., Phase TransferCatalysis, pages 37-45 and 86-93, Verlag Chemie, Weinheim 1980.

The phase transfer catalysts are advantageously used in amounts of from1 to 10, preferably from 3 to 5%, by volume, based on the volume of thereaction mixture.

The reaction of the optically active alkylating agent V with thehydroximide VI is carried out in general at from 0° to 140° C.,preferably from 2° to 100° C., in particular from 40° to 80° C. In anadvantageous procedure, the hydroximide VI is initially taken togetherwith the base in the solvent, and the alkylating agent V is metered intothis solution. It may prove advantageous if the hydroximide is added ata lower temperature, for example at from 0° to 50° C., and the reactionmixture is heated to the actual reaction temperature only after thisaddition.

After the end of the reaction, water is expediently added to the cooledreaction mixture, the resulting hydroxylamine derivatives VII separatingout as a crystalline solid or as an oil. The hydroxylamine derivativesobtained in this manner can, if desired, be further purified byrecrystallization or by extraction.

The hydroxylamine derivative VII may be temporarily stored orimmediately converted into the optically active hydroxylamines IIIhaving a free amino group.

This conversion can be carried out by a conventional process, asdescribed, for example, in DE-A 36 15 973 and the publications citedtherein. The process according to DE-A 36 15 973, in which the opticallyactive hydroxylamines III were liberated by means of ethanolamine, arepreferably used. Liberation of the hydroxylamines III with the aid ofother bases, such as aqueous mineral bases, with a mines, hydrazines orhydroxylamines or by means of aqueous acids is also possible.

The optically active hydroxylamines III can be isolated from thereaction mixtures obtained in these processes by means of conventionalmethods of working up, for example by extraction or by crystallization.To increase the tendency of these hydroxylamines III to crystallize, itmay often be advantageous to convert them into their salts with mineralacids or organic acids. For this purpose, in general dilute solutions ofthese acids are reacted with the hydroxylamine derivatives, expedientlyin roughly equivalent amounts. The hydroxyl ammonium salts obtained can,as the optically active hydroxylamines III (with free amino group), bedirectly further processed to give the optically active cyclohexenoneoxime ethers of the formula I or, if desired, can also be stored.

The optical purity of the intermediates III and of the cyclohexenoneoxime ether I depends on the optical purity of the carbinols IV oralkylating agents V used. The carbinols IV and the alkylating agents Vare preferably used as mixtures, containing at least 50 mol % of Risomers, so that, in the preparation of the optically activehydroxylamines III and of the optically active cyclohexenone oximeethers I, isomer mixtures containing at least 50, preferably from 90 to100, mol % of isomers having the R-configuration at themethyl-substituted carbon atom (in the oxime ether moiety) are obtainedin each case.

Depending on the substituents, the optically active cyclohexenone oximeethers I may be obtained in the preparation also in the form of the E/Zisomer mixtures, the isomers differing due to the position of the oximeether moiety relative to R¹. The E and Z isomers can, if desired, beseparated by a conventional method, for example by chromatography or bycrystallization.

The optically active cyclohexenone oxime ethers I may be written in aplurality of tautomeric forms, and the present invention relates to allof these forms.

The collective terms used in the definition of the substituents

halogen

C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, C₁ -C₄ -alkylthio, C₁ -C₄ -haloalkyl,

C₂ -C₆ -alkenyl, C₂ -C₆ -alkenyloxy,

C₃ -C₆ -alkenyl, C₃ -C₆ -alkenyloxy, C₃ -C₆ -alkynyl, C₃ -C₆-alkynyloxy,

C₁ -C₆ -acyl are shorthand for an individual listing of the specificgroup members. All the alkyl, alkoxy, alkylthio, haloalkyl, alkenyl,alkenyloxy, alkynyl and alkynyloxy moieties may be straight-chain orbranched. The haloalkyl moieties may carry identical or differenthalogen atoms.

Specific examples are as follows:

halogen: fluorine, chlorine, bromine and iodine;

C₁ -C₄ -alkyl: methyl, ethyl, n-propyl, 1-methylethyl, n-butyl,1-methylpropyl, 2-methylpropyl and 1,1-dimethylethyl;

C₁ -C₄ -alkoxy: methoxy, ethoxy, n-propoxy, 1-methylethoxy, n-butoxy,1-methylpropoxy, 2-methylpropoxy and 1,1-dimethylethoxy;

C₁ -C₄ -alkylthio: methylthio, ethylthio, n-propylthio,1-methylethylthio, n-butylthio, 1-methylpropylthio, 2-methylpropylthioand 1,1-dimethylethylthio;

C₁ -C₄ -haloalkyl: fluoromethyl, difluoromethyl, trifluoromethyl,chlorodifluoromethyl, dichlorofluoromethyl, trichloromethyl,1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl,2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl,2,2,2-trichloroethyl and pentafluoroethyl;

C₂ -C₆ -alkenyl: ethenyl and C₃ -C₆ -alkenyl, such as 1-propenyl,2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl,1-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-1-propenyl,2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl,1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl,1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl,1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl,1,1-dimethyl-2-propenyl, 1,2-dimethyl-1-propenyl,1,2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl,1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl,1-methyl-1-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl,4-methyl-1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl,3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl,2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl,1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl,4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3butenyl,1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl,1,3-dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl,2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl,2,3-dimethyl-3-butenyl, 3,3-dimethyl-1-butenyl, 1-ethyl-1-butenyl,1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1-butenyl,2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl,1-ethyl-1-methyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl and1-ethyl-2-methyl-2-propenyl;

C₂ -C₆ -alkenyloxy: ethenyloxy and C₃ -C₆ -alkenyloxy, such as2-propenyloxy, 2-butenyloxy, 3-butenyloxy, 1-methyl-2-propenyloxy,2-methyl-2-propenyloxy, 2-pentenyloxy, 3-pentenyloxy, 4-pentenyloxy,1-methyl-2-butenyloxy, 2-methyl-2-butenyloxy, 3-methyl-2-butenyloxy,1-methyl-3-butenyloxy, 2-methyl-3-butenyloxy, 3-methyl-3-butenyloxy,1,1-dimethyl-2-propenyloxy, 1,2-dimethyl-2-propenyloxy,1-ethyl-2-propenyloxy, 2-hexenyloxy, 3-hexenyloxy, 4-hexenyloxy,5-hexenyloxy, 1-methyl-2-pentenyloxy, 2-methyl-2-hexenyloxy,3-methyl-2-pentenyloxy, 4-methyl-2-pentenyloxy, 1-methyl-3-pentenyloxy,2-methyl-3-pentenyloxy, 3-methyl-3-pentenyloxy, 4-methyl-3-pentenyloxy,1-methyl-4-pentenyloxy, 2-methyl-4-pentenyloxy, 3-methyl-4-pentenyloxy,4-methyl-4-pentenyloxy, 1,1-dimethyl-2-butenyloxy,1,2-dimethylpentenyloxy, 2-butenyloxy, 1,2-dimethyl-3-butenyloxy,1,3-dimethyl-2-butenyloxy, 1,3-dimethyl-3-butenyloxy,2,2-dimethyl-3-butenyloxy, 2,3-dimethyl-2-butenyloxy,2,3-dimethyl-3-butenyloxy, 1-ethyl-2-butenyloxy, 1-ethyl-3-butenyloxy,2-ethyl-2-butenyloxy, 2-ethyl-3-butenyloxy,1,1,2-trimethyl-2-propenyloxy, 1-ethyl-1-methyl-2-propenyloxy and1-ethyl-2-methyl-2-propenyloxy.

In view of their herbicidal activity, preferred mixtures of opticallyactive cyclohexenones of the formula I are those in which

R¹ is C₁ -C₆ -alkyl, such as methyl, ethyl, n-propyl, n-butyl, n-pentyland n-hexyl, preferably ethyl and propyl;

Z is one of the following groups: ##STR11## particularly preferably##STR12##

X is halogen, such as fluorine, chlorine, bromine and iodine, perferablyfluorine, chlorine or bromine, or

C₁ -C₄ -haloalkyl, preferably difluoromethyl, trifluoromethyl,2,2,2-trifluoroethyl or pentafluoroethyl, particularly preferablyhalogen or trifluoromethyl;

m is from 0 to 3, or from 1 to 4 where all X are halogen, preferablyfrom 0 to 3;

n is from 0 to 3, or from 1 to 5 where all X are halogen, preferablyfrom 0 to 3;

R² is C₁ -C₆ -alkyl, such as methyl, ethyl, n-propyl, 1-methylethyl,n-butyl, 1-methylpropyl, 2-methylpropyl and 1,1-dimethylethyl, n-pentyl,1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl,1,2-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl,1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl,1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl,2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl,2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl,1-ethyl-1-methylpropyl and 1-ethyl-2-methylpropyl, where the alkyl groupis substituted by C₁ -C₄ -alkoxy, preferably methoxy, ethoxy,1-methylethoxy or 1,1-dimethylethoxy, or by C₁ -C₄ -alkylthio,preferably methylthio or ethylthio, preferably in the 1-, 2- or3-position, very particularly preferably 2-ethylthiopropyl;

C₃ -C₇ -cycloalkyl or C₅ -C₇ -cycloalkenyl, such as cyclopropyl,cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclopentenyl,cyclohexenyl or cycloheptenyl, where these groups may be unsubstitutedor may carry from one to three of the following substituents: C₁ -C₄-alkyl, preferably methyl, C₁ -C₄ -alkoxy, C₁ -C₄ -alkylthio and C₁ -C₄-haloalkyl,

very particularly preferably 1-methylthio-1-cyclopropyl; a 5-memberedsaturated heterocyclic structure, such as tetrahydrofuranyl,tetrahydrothienyl, dioxolanyl, dithiolanyl and oxathiolanyl, inparticular tetrahydrofuranyl, tetrahydrothienyl or dioxolanyl, wherethese rings may be unsubstituted or may carry from one to threesubstituents selected from the group consisting of C₁ -C₄ -alkyl, C₁ -C₄-alkoxy, C₁ -C₄ -alkylthio and C₁ -C₄ -haloalkyl;

a 5-membered heteroaromatic structure, such as pyrrolyl, pyrazolyl,imidazolyl, isoxazolyl, oxazolyl, isothiazolyl, thiazolyl, furanyl andthienyl, in particular isoxazolyl or furanyl, where the 5-memberedheteroaromatic structure may be unsubstituted or may carry from one tothree substituents selected from the group consisting of C₁ -C₄ -alkyl,C₁ -C₄ -alkoxy, C₁ -C₄ -alkylthio, C₁ -C₄ -haloalkyl, C₁ -C₄ -alkoxy-C₁-C₄ -alkyl, such as methoxymethyl, 2-methoxyethyl, 2-methoxypropyl,3-methoxypropyl, 2-methoxy-1-methylethyl, ethoxymethyl, 2-ethoxyethyl,2-ethoxypropyl, 3-ethoxypropyl, 2-ethoxy-1-methylethyl and1-ethoxy-1-methylethyl, preferably methoxyethyl and ethoxyethyl, C₂ -C₆-alkenyl, such as ethenyl, and C₃ -C₆ -alkenyl, preferably1-methylethen-1-yl, C₂ -C₆ -alkenyloxy, such as ethenyloxy, and C₃ -C₆-alkenyloxy, in particular 1-methylethen-1-yloxy;

a 6-membered or 7-membered heterocyclic structure which

a) may be saturated, eg. tetrahydropyran-3-yl, tetrahydropyran-4-yl,tetrahydrothiopyran-3-yl, tetrahydrothiopyran-4-yl and dioxepan-5-yl, or

b) may be mono- or diunsaturated, eg. dihydropyran-3-yl,dihydropyran-4-yl, dihydrothiopyran-3-yl or dihydrothiopyran-4-yl,

where the heterocyclic structures may be unsubstituted or may carry fromone to three substituents selected from the group consisting ofhydroxyl, halogen, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, C₁ -C₄ -alkylthio andC₁ -C₄ -haloalkyl, very particularly preferably tetrahydropyran-3-yl,tetrahydropyran-4-yl and tetrahydrothiopyran-3-yl; phenyl or pyridyl,both of which may be unsubstituted or may carry from one to threesubstituents selected from the group consisting of C₁ -C₄ -alkyl, C₁ -C₄-alkoxy, C₁ -C₄ -alkylthio, C₁ -C₄ -haloalkyl, C₃ -C₆ -alkenyloxy,preferably prop-2-en-1-yloxy or but-2-en-1-yloxy, C₃ -C₆ -alkynyloxy,such as 2-propynyloxy, 2-butynyloxy, 3-butynyloxy,1-methyl-2-propynyloxy, 2-pentynyloxy, 3-pentynyloxy, 4-pentynyloxy,1-methyl-3-butynyloxy, 2-methyl-3-butynyloxy, 1-methyl-2-butynyloxy,1,1-dimethyl-2-propynyloxy, 1-ethyl-2-propynyloxy, 2-hexynyloxy,3-hexynyloxy, 4-hexynyloxy, 5-hexynyloxy, 1-methyl-2-pentynyloxy,1-methyl-3-pentynyloxy, 1-methyl-4-pentynyloxy, 2-methyl-3-pentynyloxy,2-methyl-4-pentynyloxy, 3-methyl-4-pentynyloxy, 4-methyl-4-pentynyloxy,1,1-dimethyl-2-butnynyloxy, 1,1-dimethyl-3-butynyloxy,1,2-dimethyl-3-butynyloxy, 2,2-dimethyl-3-butynyloxy,1-ethyl-2-butynyloxy, 1-ethyl-3-butynyloxy, 2-ethyl-3-butynyloxy and1-ethyl-1-methyl-2-propynyloxy, preferably 2-propynyloxy or2-butynyloxy; one of the three substituents on the phenyl or pyridylring may furthermore be an amino group --NR^(a) R^(b), where

R^(a) is hydrogen,

C₁ -C₄ -alkyl, preferably methyl or ethyl,

C₃ -C₆ -alkenyl, preferably prop-2-en-1-yl or but-2-en-1-yl, or

C₃ -C₆ -alkynyl, preferably prop-2-yn-1-yl or but-2-yn-1-yl, and

R^(b) is hydrogen,

C₁ -C₄ -alkyl, preferably methyl or ethyl,

C₃ -C₆ -alkenyl, preferably prop-2-en-1-yl or but-2-en-1-yl,

C₃ -C₆ -alkynyl, preferably prop-2-yn-1-yl or but-2-yn-1-yl, or

C₁ -C₆ -acyl, such as acetyl, propionyl, n-butyryl, 2-methylpropionyl,n-pentanoyl, 2-methylbutyryl, 2-methylbutyryl, 2,2-dimethylpropionyl,n-hexanoyl, 2-methylpentanoyl, 3-methylpentanoyl, 4-methylpentanoyl,2,2-dimethylbutyryl, 2,3-dimethylbutyryl, 3,3-dimethylbutyryl and2-ethylbutyryl, preferably acetyl or propionyl, or benzoyl which may beunsubstituted or may in turn carry from one to three radicals selectedfrom the group consisting of nitro, cyano, halogen, preferably fluorine,chlorine and bromine, C₁ -C₄ -alkyl, preferably methyl, C₁ -C₄ -alkoxy,preferably methoxy and ethoxy, C₁ -C₄ -alkylthio, preferably methylthio,and C₁ -C₄ -haloalkyl, preferably trifluoromethyl.

Suitable salts of the compounds of the formula I are agriculturallyuseful salts, for example alkali metal salts, in particular the sodiumor potassium salt, alkaline earth metal salts, in particular thecalcium, magnesium or barium salt, manganese, copper, zinc or iron saltand ammonium, phosphonium, sulfonium or sulfoxonium salts, for exampleammonium salts, tetraalkylammonium salts, benzyltrialkylammonium salts,trialkylsulfonium salts or trialkylsulfoxonium salts.

Esters of C₁ -C₁₀ -carboxylic acids are understood as being inparticular esters of C₁ -C₄ -alkanecarboxylic acids, such asmethanecarboxylic acid (acetic acid), ethanecarboxylic acid (propionicacid), propanecarboxylic acid (butyric acid), 1-methylethanecarboxylicacid (isobutyric acid), butanecarboxylic acid, 1-methylpropanecarboxylicacid, 2-methylpropanecarboxylic acid, 1,1-dimethylethanecarboxylic acid,pentanecarboxylic acid, 1-methylbutanecarboxylic acid,2-methylbutanecarboxylic acid, 3-methylbutanecarboxylic acid,1,1-dimethylpropanecarboxylic acid, 1,2-dimethylpropanecarboxylic acid,2,2-dimethylpropanecarboxylic acid, 1-ethylpropanecarboxylic acid,benzoic acid and halogen-substituted benzoic acids, hexanecarboxylicacid, 1-methylpentanecarboxylic acid, 2-methylpentanecarboxylic acid,3-methylpentanecarboxylic acid, 4-methylpentanecarboxylic acid,1,1-dimethylbutanecarboxylic acid, 1,2-dimethylbutanecarboxylic acid,1,3-dimethylbutanecarboxylic acid, 2,2-dimethylbutanecarboxylic acid,2,3-dimethylbutanecarboxylic acid, 3,3-dimethylbutanecarboxylic acid,1-ethylbutanecarboxylic acid, 2-ethylbutanecarboxylic acid,1,1,2-trimethylpropanecarboxylic acid, 1,2,2-trimethylpropanecarboxylicacid, 1-ethyl-1-methylpropanecarboxylic acid and1-ethyl-2-methylpropanecarboxylic acid.

PREPARATION EXAMPLES2-[1-[2-[4-(2,4-Dichlorophenoxy)phenoxy]propyloximino]-propyl]-3-hydroxy-5-(2H-tetrahydropyran-4-yl)-2-cyclo-hexen-1-one(4.04)

A mixture of 0.71 g (2.8 mmol) of3-hydroxy-2-propionyl-5-(2H-tetrahydropyran-4-yl)-2-cyclohexen-1-one,1.2 g (2.8 mmol) of 75% strength0-[2-[4-(2,4-dichlorophenoxy)phenoxy]propylhydroxylamine and 100 ml ofmethanol was stirred for 24 hours at room temperature and then worked upin a known manner to give the product. Yield: 69%

¹ H-NMR (200 MHz, in CDCl₃): δ [ppm]=1.15 (t, 3H), 1.20-1.45 (m, 6H),1.65 (m, 2H), 1.90 (m, 1H), 2.25 (m, 2H), 2.60 (m, 2H); 2.85 (m, 2H),3.35 (m, 2H), 4.00 (m, 2H), 4.25 (m, 2H), 4.60 (m, 1H), 6.80-7.55 (m,7H).

INTERMEDIATE 0-[2-[4-(2,4-Dichlorophenoxy)phenoxy]propylhydroxylamine

7.5 g (0.043 mol) of diethyl azodicarboxylate were slowly added dropwiseto a solution of 7.0 g (0.043 mol) of N-hydroxyphthalimide, 9.4 g (0.038mol) of triphenylphosphine and 11.4 g (0.036 mol) of2-[4-(2,4-dichlorophenoxy)phenoxy]-propan-1-ol (Z. Naturforsch. 37 B(1982), 912) in 250 ml of tetrahydrofuran. After a weakly exothermicreaction, working up was carried out after 15 hours in a known manner togive 16.3 g of the intermediateN-[2-[4-(2,4-dichlorophenoxy)phenoxy]propoxy]phthalimide.

200 ml of ethanolamine were then slowly added to this crude phthalimideproduct. After 3.5 hours at 60° C., the reaction mixture was poured intoice water and extracted with methylene chloride, and the combinedorganic phases were washed with water, dried over sodium sulfate andevaporated down under reduced pressure. Yield: 9.7 g (62% corrected) of75% strength hydroxylamine (1.03).

¹ H-NMR (200 MHz, in CDCl₃); δ [ppm]=1.30 (d, 3H), 3.80 (m, 2H), 4.65(m, 1H), 5.55 (bs, 1H), 6.80-7.50 (m, 7H).

Novel hydroxylamines III are listed in Table 1 below. Tables 2 to 17contain novel cyclohexenone oxime ethers I.

                                      TABLE 1                                     __________________________________________________________________________     ##STR13##                           III                                                                    Phys. data                                                                    (.sup.1 H-NMR [ppm],                                                          Rotational                                      No. Z                 *.sup.) Configuration                                                                 value [α].sub.D .sup.25)                  __________________________________________________________________________    1.01                                                                              4-Chlorophenyl    (RS)    4.20 (m, 2H),                                                                 4.60 (m, 1H),                                                                 6.80-7.35                                                                     (2m, 8H)                                        1.02                                                                              4-Chlorophenyl    (R)                                                     1.03                                                                              2,4-Dichlorophenyl                                                                              (RS)    1.30 (d, 3H),                                                                 3.80 (m, 2H),                                                                 4.65 (m, 1H),                                                                 5.55 (bs, 1H),                                                                6.80-7.50(m, 7H)                                1.04                                                                              2,4-Dichlorophenyl                                                                              (R)                                                     1.05                                                                              5-Trifluoromethyl-2-pyridyl                                                                     (RS)                                                    1.06                                                                              5-Trifluoromethyl-2-pyridyl                                                                     (R)                                                     1.07                                                                              3-Chloro-5-trifluoromethyl-2-pyridyl                                                            (RS)                                                    1.08                                                                              3-Chloro-5-trifluoromethyl-2-pyridyl                                                            (R)                                                     1.09                                                                              5-Chloro-3-fluoro-2-pyridyl                                                                     (RS)                                                    1.10                                                                              5-Chloro-3-fluoro-2-pyridyl                                                                     (R)                                                     1.11                                                                               ##STR14##        (RS)                                                    1.12                                                                               ##STR15##        (R)                                                     1.13                                                                               ##STR16##        (RS)                                                    1.14                                                                               ##STR17##        (R)                                                     1.15                                                                               ##STR18##        (RS)                                                    1.16                                                                               ##STR19##        (R)                                                     __________________________________________________________________________

                                      TABLE 2                                     __________________________________________________________________________     ##STR20##                             I                                                                 Phys. data (Rotational                                                        value [α].sub.D .sup.25 ;                    No.  R.sup.1                                                                            R.sup.2          .sup.1 H-NMR [ppm])                                __________________________________________________________________________    2.01 Ethyl                                                                              (RS)-2H-Tetrahydropyran-3-yl                                                                   3.80-4.00 (m, 2H),                                                            4.20 (m, 2H),                                                                 4.60 (m, 1H),                                                                 6.80-7.35 (2m, 8H)                                 2.02 Ethyl                                                                              (R)-2H-Tetrahydropyran-3-yl                                         2.03 Ethyl                                                                              (S)-2H-Tetrahydropyran-3-yl                                         2.04 Ethyl                                                                              2H-Tetrahydropyran-4-yl                                                                        4.00 (m, 2H), 4.20                                                            (m, 2H), 4.60                                                                 (m, 1H), 6.80-7.35                                                            (2m, 8H)                                           2.05 Ethyl                                                                              (RS)-2H-Tetrahydrothiopy-                                                                      4.20 (m, 2H), 4.60                                           ran-3-yl         (m, 1H), 6.80-7.35                                                            (2m, 8H)                                           2.06 Ethyl                                                                              (R)-2H-Tetrahydrothiopyran-3-yl                                     2.07 Ethyl                                                                              (S)-2H-Tetrahydrothiopyran-3-yl                                     2.08 Propyl                                                                             (RS)-2H-Tetrahydropyran-3-yl                                                                   3.80-4.00 (m, 2H),                                                            4.20 (m, 2H), 4.60                                                            (m, 1H) 6.80-7.35                                                             (2m, 8H)                                           2.09 Propyl                                                                             (R)-2H-Tetrahydropyran-3-yl                                         2.10 Propyl                                                                             (S)-2H-Tetrahydropyran-3-yl                                         2.11 Propyl                                                                             2H-Tetrahydropyran-4-yl                                                                        4.00 (m, 2H), 4.20                                                            (m, 2H), 4.60                                                                 (m, 1H), 6.80-7.35                                                            (2m, 8H)                                           2.12 Propyl                                                                             (RS)-2H-Tetrahydrothiopy-                                                                      4.20 (m, 2H), 4.60                                           ran-3-yl         (m, 1H) 6.80-7.35                                                             (2m, 8H)                                           2.13 Propyl                                                                             (R)-2H-Tetrahydrothiopyran-3-yl                                     2.14 Propyl                                                                             (S)-2H-Tetrahydrothiopyran-3-yl                                     2.15 Ethyl                                                                              Phenyl                                                              2.16 Ethyl                                                                              2,4,6-Trimethylphenyl                                               2.17 Ethyl                                                                              4-(Prop-2-ynyloxy)phenyl                                            2.18 Propyl                                                                             4-Fluoro-3-nitrophenyl                                              2.19 Propyl                                                                             (RS)-2-(Ethylthio)prop-1-yl                                         2.20 Ethyl                                                                              1-Methylthiocycloprop-1-yl                                          2.21 Ethyl                                                                              1,3-Dimethylpyrazol-5-yl                                            2.22 Propyl                                                                             3-Isopropylisoxazol-5-yl                                            2.23 Propyl                                                                             (RS)-Cyclohex-3-en-1-yl                                             __________________________________________________________________________     (*.sup.) Racemate; RS configuration)                                     

                                      TABLE 3                                     __________________________________________________________________________     ##STR21##                             I                                                                 Phys. data (Rotational                                                        value [α].sub.D .sup.25 ;                    No.  R.sup.1                                                                            R.sup.2          .sup.1 H-NMR [ppm])                                __________________________________________________________________________    3.01 Ethyl                                                                              (RS)-2H-Tetrahydropyran-3-yl                                        3.02 Ethyl                                                                              (R)-2H-Tetrahydropyran-3-yl                                         3.03 Ethyl                                                                              (S)-2H-Tetrahydropyran-3-yl                                         3.04 Ethyl                                                                              2H-Tetrahydropyran-4-yl                                             3.05 Ethyl                                                                              (RS)-2H-Tetrahydrothiopy-                                                     ran-3-yl                                                            3.06 Ethyl                                                                              (R)-2H-Tetrahydrothiopyran-3-yl                                     3.07 Ethyl                                                                              (S)-2H-Tetrahydrothiopyran-3-yl                                     3.08 Propyl                                                                             (RS)-2H-Tetrahydropyran-3-yl                                        3.09 Propyl                                                                             (R)-2H-Tetrahydropyran-3-yl                                         3.10 Propyl                                                                             (S)-2H-Tetrahydropyran-3-yl                                         3.11 Propyl                                                                             2H-Tetrahydropyran-4-yl                                             3.12 Propyl                                                                             (RS)-2H-Tetrahydrothiopy-                                                     ran-3-yl                                                            3.13 Propyl                                                                             (R)-2H-Tetrahydrothiopyran-3-yl                                     3.14 Propyl                                                                             (S)-2H-Tetrahydrothiopyran-3-yl                                     3.15 Ethyl                                                                              Phenyl                                                              3.16 Ethyl                                                                              2,4,6-Trimethylphenyl                                               3.17 Ethyl                                                                              4-(Prop-2-ynyloxy)phenyl                                            3.18 Propyl                                                                             4-Fluoro-3-nitrophenyl                                              3.19 Propyl                                                                             (RS)-2-(Ethylthio)prop-1-yl                                         3.20 Ethyl                                                                              1-Methylthiocycloprop-1-yl                                          3.21 Ethyl                                                                              1,3-Dimethylpyrazol-5-yl                                            3.22 Propyl                                                                             3-Isopropylisoxazol-5-yl                                            3.23 Propyl                                                                             (RS)-Cyclohex-3-en-1-yl                                             __________________________________________________________________________     (*.sup.) predominantly R configuration)                                  

                                      TABLE 4                                     __________________________________________________________________________     ##STR22##                             I                                                                 Phys. data (Rotational                                                        value [α].sub.D .sup.25 ;                    No.  R.sup.1                                                                            R.sup.2          .sup.1 H-NMR [ppm])                                __________________________________________________________________________    4.01 Ethyl                                                                              (RS)-2H-Tetrahydropyran-3-yl                                                                   3.80-4.00 (m, 2H),                                                            4.25 (m, 2H), 4.60                                                            (m, 1H), 6.80-7.55                                                            (m, 7H)                                            4.02 Ethyl                                                                              (R)-2H-Tetrahydropyran-3-yl                                         4.03 Ethyl                                                                              (S)-2H-Tetrahydropyran-3-yl                                         4.04 Ethyl                                                                              2H-Tetrahydropyran-4-yl                                                                        4.00 (m, 2H), 4.25                                                            (m, 2H), 4.60                                                                 (m, 1H), 6.80-7.55                                                            (m, 7H)                                            4.05 Ethyl                                                                              (RS)-2H-Tetrahydrothiopy-                                                                      4.25 (m, 2H), 4.60                                           ran-3-yl         (m, 1H), 6.80-7.55                                                            (m, 7H)                                            4.06 Ethyl                                                                              (R)-2H-Tetrahydrothiopy-                                                      ran-3-yl                                                            4.07 Ethyl                                                                              (S)-2H-Tetrahydrothiopy-                                                      ran-3-yl                                                            4.08 Propyl                                                                             (RS)-2H-Tetrahydropyran-3-yl                                                                   3.80-4.00 (m, 2H),                                                            4.25 (m, 2H),                                                                 4.60 (m, 1H),                                                                 6.80-7.55 (m, 7H)                                  4.09 Propyl                                                                             (R)-2H-Tetrahydropyran-3-yl                                         4.10 Propyl                                                                             (S)-2H-Tetrahydropyran-3-yl                                         4.11 Propyl                                                                             2H-Tetrahydropyran-4-yl                                                                        4.00 (m, 2H), 4.25                                                            (m, 2H), 4.60                                                                 (m, 1H), 6.80-7.55                                                            (m, 7H)                                            4.12 Propyl                                                                             (RS)-2H-Tetrahydrothiopy-                                                                      4.25 (m, 2H), 4.60                                           ran-3-yl         (m, 1H), 6.80-7.55                                                            (m, 7H)                                            4.13 Propyl                                                                             (R)-2H-Tetrahydrothiopy-                                                      ran-3-yl                                                            4.14 Propyl                                                                             (S)-2H-Tetrahydrothiopy-                                                      ran-3-yl                                                            4.15 Ethyl                                                                              Phenyl                                                              4.16 Ethyl                                                                              2,4,6-Trimethylphenyl                                               4.17 Ethyl                                                                              4-(Prop-2-ynyloxy)phenyl                                            4.18 Propyl                                                                             4-Fluoro-3-nitrophenyl                                              4.19 Propyl                                                                             (RS)-2-(Ethylthio)prop-1-yl                                         4.20 Ethyl                                                                              1-Methylthiocycloprop-1-yl                                          4.21 Ethyl                                                                              1,3-Dimethylpyrazol-5-yl                                            4.22 Propyl                                                                             3-Isopropylisoxazol-5-yl                                            4.23 Propyl                                                                             (RS)-Cyclohex-3-en-1-yl                                             __________________________________________________________________________     (*.sup.) Racemate; RS configuration)                                     

                                      TABLE 5                                     __________________________________________________________________________     ##STR23##                             I                                                                 Phys. data (Rotational                                                        value [α].sub.D .sup.25 ;                    No.  R.sup.1                                                                            R.sup.2          .sup.1 H-NMR [ppm])                                __________________________________________________________________________    5.01 Ethyl                                                                              (RS)-2H-Tetrahydropyran-3-yl                                        5.02 Ethyl                                                                              (R)-2H-Tetrahydropyran-3-yl                                         5.03 Ethyl                                                                              (S)-2H-Tetrahydropyran-3-yl                                         5.04 Ethyl                                                                              2H-Tetrahydropyran-4-yl                                             5.05 Ethyl                                                                              (RS)-2H-Tetrahydrothiopy-                                                     ran-3-yl                                                            5.06 Ethyl                                                                              (R)-2H-Tetrahydrothiopyran-3-yl                                     5.07 Ethyl                                                                              (S)-2H-Tetrahydrothiopyran-3-yl                                     5.08 Propyl                                                                             (RS)-2H-Tetrahydropyran-3-yl                                        5.09 Propyl                                                                             (R)-2H-Tetrahydropyran-3-yl                                         5.10 Propyl                                                                             (S)-2H-Tetrahydropyran-3-yl                                         5.11 Propyl                                                                             2H-Tetrahydropyran-4-yl                                             5.12 Propyl                                                                             (RS)-2H-Tetrahydrothiopy-                                                     ran-3-yl                                                            5.13 Propyl                                                                             (R)-2H-Tetrahydrothiopyran-3-yl                                     5.14 Propyl                                                                             (S)-2H-Tetrahydrothiopyran-3-yl                                     5.15 Ethyl                                                                              Phenyl                                                              5.16 Ethyl                                                                              2,4,6-Trimethylphenyl                                               5.17 Ethyl                                                                              4-(Prop-2-ynyloxy)phenyl                                            5.18 Propyl                                                                             4-Fluoro-3-nitrophenyl                                              5.19 Propyl                                                                             (RS)-2-(Ethylthio)prop-1-yl                                         5.20 Ethyl                                                                              1-Methylthiocycloprop-1-yl                                          5.21 Ethyl                                                                              1,3-Dimethylpyrazol-5-yl                                            5.22 Propyl                                                                             3-Isopropylisoxazol-5-yl                                            5.23 Propyl                                                                             (RS)-Cyclohex-3-en-1-yl                                             __________________________________________________________________________     (*.sup.) predominantly R configuration)                                  

                                      TABLE 6                                     __________________________________________________________________________     ##STR24##                              I                                                                 Phys. data (Rotational                                                        value [α].sub.D .sup.25 ;                   No.  R.sup.1                                                                            R.sup.2           .sup.1 H-NMR [ppm]                                __________________________________________________________________________    6.01 Ethyl                                                                              (RS)-2H-Tetrahydropyran-3-yl                                        6.02 Ethyl                                                                              (R)-2H-Tetrahydropyran-3-yl                                         6.03 Ethyl                                                                              (S)-2H-Tetrahydropyran-3-yl                                         6.04 Ethyl                                                                              2H-Tetrahydropyran-4-yl                                             6.05 Ethyl                                                                              (RS)-2H-Tetrahydrothiopy-                                                     ran-3-yl                                                            6.06 Ethyl                                                                              (R)-2H-Tetrahydrothiopy-                                                      ran-3-yl                                                            6.07 Ethyl                                                                              (S)-2H-Tetrahydrothiopy-                                                      ran-3-yl                                                            6.08 Propyl                                                                             (RS)-2H-Tetrahydropyran-3-yl                                        6.09 Propyl                                                                             (R)-2H-Tetrahydropyran-3-yl                                         6.10 Propyl                                                                             (S)-2H-Tetrahydropyran-3-yl                                         6.11 Propyl                                                                             2H-Tetrahydropyran-4-yl                                             6.12 Propyl                                                                             (RS)-2H-Tetrahydrothiopy-                                                     ran-3-yl                                                            6.13 Propyl                                                                             (R)-2H-Tetrahydrothiopy-                                                      ran-3-yl                                                            6.14 Propyl                                                                             (S)-2H-Tetrahydrothiopy-                                                      ran-3-yl                                                            6.15 Ethyl                                                                              Phenyl                                                              6.16 Ethyl                                                                              2,4,6-Trimethylphenyl                                               6.17 Ethyl                                                                              4-(Prop-2-ynyloxy)phenyl                                            6.18 Propyl                                                                             4-Fluoro-3-nitrophenyl                                              6.19 Propyl                                                                             (RS)-2-(Ethylthio)prop-1-yl                                         6.20 Ethyl                                                                              1-Methylthiocycloprop-1-yl                                          6.21 Ethyl                                                                              1,3-Dimethylpyrazol-5-yl                                            6.22 Propyl                                                                             3-Isopropylisoxazol-5-yl                                            6.23 Propyl                                                                             (RS)-Cyclohex-3-en-1-yl                                             __________________________________________________________________________     (*.sup.) Racemate; RS configuration)                                     

                                      TABLE 7                                     __________________________________________________________________________     ##STR25##                              I                                                                 Phys. data (Rotational                                                        value [α].sub.D .sup.25 ;                   No.  R.sup.1                                                                            R.sup.2           .sup.1 H-NMR [ppm]                                __________________________________________________________________________    7.01 Ethyl                                                                              (RS)-2H-Tetrahydropyran-3-yl                                        7.02 Ethyl                                                                              (R)-2H-Tetrahydropyran-3-yl                                         7.03 Ethyl                                                                              (S)-2H-Tetrahydropyran-3-yl                                         7.04 Ethyl                                                                              2H-Tetrahydropyran-4-yl                                             7.05 Ethyl                                                                              (RS)-2H-Tetrahydrothiopy-                                                     ran-3-yl                                                            7.06 Ethyl                                                                              (R)-2H-Tetrahydrothiopy-                                                      ran-3-yl                                                            7.07 Ethyl                                                                              (S)-2H-Tetrahydrothiopy-                                                      ran-3-yl                                                            7.08 Propyl                                                                             (RS)-2H-Tetrahydropyran-3-yl                                        7.09 Propyl                                                                             (R)-2H-Tetrahydropyran-3-yl                                         7.10 Propyl                                                                             (S)-2H-Tetrahydropyran-3-yl                                         7.11 Propyl                                                                             2H-Tetrahydropyran-4-yl                                             7.12 Propyl                                                                             (RS)-2H-Tetrahydrothiopy-                                                     ran-3-yl                                                            7.13 Propyl                                                                             (R)-2H-Tetrahydrothiopy-                                                      ran-3-yl                                                            7.14 Propyl                                                                             (S)-2H-Tetrahydrothiopy-                                                      ran-3-yl                                                            7.15 Ethyl                                                                              Phenyl                                                              7.16 Ethyl                                                                              2,4,6-Trimethylphenyl                                               7.17 Ethyl                                                                              4-(Prop-2-ynyloxy)phenyl                                            7.18 Propyl                                                                             4-Fluoro-3-nitrophenyl                                              7.19 Propyl                                                                             (RS)-2-(Ethylthio)prop-1-yl                                         7.20 Ethyl                                                                              1-Methylthiocycloprop-1-yl                                          7.21 Ethyl                                                                              1,3-Dimethylpyrazol-5-yl                                            7.22 Propyl                                                                             3-Isopropylisoxazol-5-yl                                            7.23 Propyl                                                                             (RS)-Cyclohex-3-en-1-yl                                             __________________________________________________________________________     (*.sup.) predominantly R configuration)                                  

                                      TABLE 8                                     __________________________________________________________________________     ##STR26##                              I                                                                 Phys. data (Rotational                                                        value [α].sub.D .sup.25 ;                   No.  R.sup.1                                                                            R.sup.2           .sup.1 H-NMR [ppm]                                __________________________________________________________________________    8.01 Ethyl                                                                              (RS)-2H-Tetrahydropyran-3-yl                                        8.02 Ethyl                                                                              (R)-2H-Tetrahydropyran-3-yl                                         8.03 Ethyl                                                                              (S)-2H-Tetrahydropyran-3-yl-                                        8.04 Ethyl                                                                              2H-Tetrahydropyran-4-yl                                             8.05 Ethyl                                                                              (RS)-2H-Tetrahydrothiopy-                                                     ran-3-yl                                                            8.06 Ethyl                                                                              (R)-2H-Tetrahydrothiopy-                                                      ran-3-yl                                                            8.07 Ethyl                                                                              (S)-2H-Tetrahydrothiopy-                                                      ran-3-yl                                                            8.08 Propyl                                                                             (RS)-2H-Tetrahydropyran-3-yl                                        8.09 Propyl                                                                             (R)-2H-Tetrahydropyran-3-yl                                         8.10 Propyl                                                                             (S)-2H-Tetrahydropyran-3-yl                                         8.11 Propyl                                                                             2H-Tetrahydropyran-4-yl                                             8.12 Propyl                                                                             (RS)-2H-Tetrahydrothiopy-                                                     ran-3-yl                                                            8.13 Propyl                                                                             (R)-2H-Tetrahydrothiopy-                                                      ran-3-yl                                                            8.14 Propyl                                                                             (S)-2H-Tetrahydrothiopy-                                                      ran-3-yl                                                            8.15 Ethyl                                                                              Phenyl                                                              8.16 Ethyl                                                                              2,4,6-Trimethylphenyl                                               8.17 Ethyl                                                                              4-(Prop-2-ynyloxy)phenyl                                            8.18 Propyl                                                                             4-Fluoro-3-nitrophenyl                                              8.19 Propyl                                                                             (RS)-2-(Ethylthio)prop-1-yl                                         8.20 Ethyl                                                                              1-Methylthiocycloprop-1-yl                                          8.21 Ethyl                                                                              1,3-Dimethylpyrazol-5-yl                                            8.22 Propyl                                                                             3-Isopropylisoxazol-5-yl                                            8.23 Propyl                                                                             (RS)-Cyclohex-3-en-1-yl                                             __________________________________________________________________________     (*.sup.) Racemate; RS configuration)                                     

                                      TABLE 9                                     __________________________________________________________________________     ##STR27##                              I                                                                 Phys. data (Rotational                                                        value [α].sub.D .sup.25 ;                   No.  R.sup.1                                                                            R.sup.2           .sup.1 H-NMR [ppm]                                __________________________________________________________________________    9.01 Ethyl                                                                              (RS)-2H-Tetrahydropyran-3-yl                                        9.02 Ethyl                                                                              (R)-2H-Tetrahydropyran-3-yl                                         9.03 Ethyl                                                                              (S)-2H-Tetrahydropyran-n-3-yl                                       9.04 Ethyl                                                                              2H-Tetrahydropyran-4-yl                                             9.05 Ethyl                                                                              (RS)-2H-Tetrahydrothiopy-                                                     ran-3-yl                                                            9.06 Ethyl                                                                              (R)-2H-Tetrahydrothiopy-                                                      ran-3-yl                                                            9.07 Ethyl                                                                              (S)-2H-Tetrahydrothiopy-                                                      ran-3-yl                                                            9.08 Propyl                                                                             (RS)-2H-Tetrahydropyran-3-yl                                        9.09 Propyl                                                                             (R)-2H-Tetrahydropyran-3-yl                                         9.10 Propyl                                                                             (S)-2H-Tetrahydropyran-3-yl                                         9.11 Propyl                                                                             2H-Tetrahydropyran-4-yl                                             9.12 Propyl                                                                             (RS)-2H-Tetrahydrothiopy-                                                     ran-3-yl                                                            9.13 Propyl                                                                             (R)-2H-Tetrahydrothiopy-                                                      ran-3-yl                                                            9.14 Propyl                                                                             (S)-2H-Tetrahydrothiopy-                                                      ran-3-yl                                                            9.15 Ethyl                                                                              Phenyl                                                              9.16 Ethyl                                                                              2,4,6-Trimethylphenyl                                               9.17 Ethyl                                                                              4-(Prop-2-ynyloxy)phenyl                                            9.18 Propyl                                                                             4-Fluoro-3-nitrophenyl                                              9.19 Propyl                                                                             (RS)-2-(Ethylthio)prop-1-yl                                         9.20 Ethyl                                                                              1-Methylthiocycloprop-1-yl                                          9.21 Ethyl                                                                              1,3-Dimethylpyrazol-5-yl                                            9.22 Propyl                                                                             3-Isopropylisoxazol-5-yl                                            9.23 Propyl                                                                             (RS)-Cyclohex-3-en-1-yl                                             __________________________________________________________________________     (*.sup.) predominantly R configuration)                                  

                                      TABLE 10                                    __________________________________________________________________________     ##STR28##                              I                                                                 Phys. data (Rotational                                                        value [α].sub.D .sup.25 ;                   No.  R.sup.1                                                                            R.sup.2           .sup.1 H-NMR [ppm]                                __________________________________________________________________________    10.01                                                                              Ethyl                                                                              (RS)-2H-Tetrahydropyran-3-yl                                        10.02                                                                              Ethyl                                                                              (R)-2H-Tetrahydropyran-3-yl                                         10.03                                                                              Ethyl                                                                              (S)-2H-Tetrahydropyran-3-yl                                         10.04                                                                              Ethyl                                                                              2H-Tetrahydropyran-4-yl                                             10.05                                                                              Ethyl                                                                              (RS)-2H-Tetrahydrothiopy-                                                     ran-3-yl                                                            10.06                                                                              Ethyl                                                                              (R)-2H-Tetrahydrothiopy-                                                      ran-3-yl                                                            10.07                                                                              Ethyl                                                                              (S)-2H-Tetrahydrothiopy-                                                      ran-3-yl                                                            10.08                                                                              Propyl                                                                             (RS)-2H-Tetrahydropyran-3-yl                                        10.09                                                                              Propyl                                                                             (R)-2H-Tetrahydropyran-3-yl                                         10.10                                                                              Propyl                                                                             (S)-2H-Tetrahydropyran-3-yl                                         10.11                                                                              Propyl                                                                             2H-Tetrahydropyran-4-yl                                             10.12                                                                              Propyl                                                                             (RS)-2H-Tetrahydrothiopy-                                                     ran-3-yl                                                            10.13                                                                              Propyl                                                                             (R)-2H-Tetrahydrothiopy-                                                      ran-3-yl                                                            10.14                                                                              Propyl                                                                             (S)-2H-Tetrahydrothiopy-                                                      ran-3-yl                                                            10.15                                                                              Ethyl                                                                              Phenyl                                                              10.16                                                                              Ethyl                                                                              2,4,6-Trimethylphenyl                                               10.17                                                                              Ethyl                                                                              4-(Prop-2-ynyloxy)phenyl                                            10.18                                                                              Propyl                                                                             4-Fluoro-3-nitrophenyl                                              10.19                                                                              Propyl                                                                             (RS)-2-(Ethylthio)prop-1-yl                                         10.20                                                                              Ethyl                                                                              1-Methylthiocycloprop-1-yl                                          10.21                                                                              Ethyl                                                                              1,3-Dimethylpyrazol-5-yl                                            10.22                                                                              Propyl                                                                             3-Isopropylisoxazol-5-yl                                            10.23                                                                              Propyl                                                                             (RS)-Cyclohex-3-en-1-yl                                             __________________________________________________________________________     (*.sup.) Racemate; RS configuration)                                     

                                      TABLE 11                                    __________________________________________________________________________     ##STR29##                             I                                                                  Phys. data (Rotational                                                        value [α].sub.D .sup.25 ;                   No.  R.sup.1                                                                            R.sup.2           .sup.1 H-NMR [ppm]                                __________________________________________________________________________    11.01                                                                              Ethyl                                                                              (RS)-2H-Tetrahydropyran-3-yl                                        11.02                                                                              Ethyl                                                                              (R)-2H-Tetrahydropyran-3-yl                                         11.03                                                                              Ethyl                                                                              (S)-2H-Tetrahydropyran-3-yl                                         11.04                                                                              Ethyl                                                                              2H-Tetrahydropyran-4-yl                                             11.05                                                                              Ethyl                                                                              (RS)-2H-Tetrahydrothiopy-                                                     ran-3-yl                                                            11.06                                                                              Ethyl                                                                              (R)-2H-Tetrahydrothiopy-                                                      ran-3-yl                                                            11.07                                                                              Ethyl                                                                              (S)-2H-Tetrahydrothiopy-                                                      ran-3-yl                                                            11.08                                                                              Propyl                                                                             (RS)-2H-Tetrahydropyran-3-yl                                        11.09                                                                              Propyl                                                                             (R)-2H-Tetrahydropyran-3-yl                                         11.10                                                                              Propyl                                                                             (S)-2H-Tetrahydropyran-3-yl                                         11.11                                                                              Propyl                                                                             2H-Tetrahydropyran-4-yl                                             11.12                                                                              Propyl                                                                             (RS)-2H-Tetrahydrothiopy-                                                     ran-3-yl                                                            11.13                                                                              Propyl                                                                             (R)-2H-Tetrahydrothiopy-                                                      ran-3-yl                                                            11.14                                                                              Propyl                                                                             (S)-2H-Tetrahydrothiopy-                                                      ran-3-yl                                                            11.15                                                                              Ethyl                                                                              Phenyl                                                              11.16                                                                              Ethyl                                                                              2,4,6-Trimethylphenyl                                               11.17                                                                              Ethyl                                                                              4-(Prop-2-ynyloxy)phenyl                                            11.18                                                                              Propyl                                                                             4-Fluoro-3-nitrophenyl                                              11.19                                                                              Propyl                                                                             (RS)-2-(Ethylthio)prop-1-yl                                         11.20                                                                              Ethyl                                                                              1-Methylthiocycloprop-1-yl                                          11.22                                                                              Ethyl                                                                              1,3-Dimethylpyrazol-5-yl                                            11.22                                                                              Propyl                                                                             3-Isopropylisoxazol-5-yl                                            11.23                                                                              Propyl                                                                             (RS)-Cyclohex-3-en-1-yl                                             __________________________________________________________________________     (*.sup.) predominantly R configuration)                                  

                                      TABLE 12                                    __________________________________________________________________________     ##STR30##                                 I                                                              Phys. data (Rotational                                                        value [α].sub.D .sup.25 ;                   No.  R.sup.1                                                                            R.sup.2           .sup.1 H-NMR [ppm]                                __________________________________________________________________________    12.01                                                                              Ethyl                                                                              (RS)-2H-Tetrahydropyran-3-yl                                        12.02                                                                              Ethyl                                                                              (R)-2H-Tetrahydropyran-3-yl                                         12.03                                                                              Ethyl                                                                              (S)-2H-Tetrahydropyran-3-yl                                         12.04                                                                              Ethyl                                                                              2H-Tetrahydropyran-4-yl                                             12.05                                                                              Ethyl                                                                              (RS)-2H-Tetrahydrothiopy-                                                     ran-3-yl                                                            12.06                                                                              Ethyl                                                                              (R)-2H-Tetrahydrothiopy-                                                      ran-3-yl                                                            12.07                                                                              Ethyl                                                                              (S)-2H-Tetrahydrothiopy-                                                      ran-3-yl                                                            12.08                                                                              Propyl                                                                             (RS)-2H-Tetrahydropyran-3-yl                                        12.09                                                                              Propyl                                                                             (R)-2H-Tetrahydropyran-3-yl                                         12.10                                                                              Propyl                                                                             (S)-2H-Tetrahydropyran-3-yl                                         12.11                                                                              Propyl                                                                             2H-Tetrahydropyran-4-yl                                             12.12                                                                              Propyl                                                                             (RS)-2H-Tetrahydrothiopy-                                                     ran-3-yl                                                            12.13                                                                              Propyl                                                                             (R)-2H-Tetrahydrothiopy-                                                      ran-3-yl                                                            12.14                                                                              Propyl                                                                             (S)-2H-Tetrahydrothiopy-                                                      ran-3-yl                                                            12.15                                                                              Ethyl                                                                              Phenyl                                                              12.16                                                                              Ethyl                                                                              2,4,6-Trimethylphenyl                                               12.17                                                                              Ethyl                                                                              4-(Prop-2-ynyloxy)phenyl                                            12.18                                                                              Propyl                                                                             4-Fluoro-3-nitrophenyl                                              12.19                                                                              Propyl                                                                             (RS)-2-(Ethylthio)prop-1-yl                                         12.20                                                                              Ethyl                                                                              1-Methylthiocycloprop-1-yl                                          12.21                                                                              Ethyl                                                                              1,3-Dimethylpyrazol-5-yl                                            12.22                                                                              Propyl                                                                             3-Isopropylisoxazol-5-yl                                            12.23                                                                              Propyl                                                                             (RS)-Cyclohex-3-en-1-yl                                             __________________________________________________________________________     (*.sup.) Racemate: RS configuration)                                     

                                      TABLE 13                                    __________________________________________________________________________     ##STR31##                                 I                                                              Phys. data (Rotational                                                        value [α].sub.D .sup.25 ;                   No.  R.sup.1                                                                            R.sup.2           .sup.1 H-NMR [ppm]                                __________________________________________________________________________    13.01                                                                              Ethyl                                                                              (RS)-2H-Tetrahydropyran-3-yl                                        13.02                                                                              Ethyl                                                                              (R)-2H-Tetrahydropyran-3-yl                                         13.03                                                                              Ethyl                                                                              (S)-2H-Tetrahydropyran-3-yl                                         13.04                                                                              Ethyl                                                                              2H-Tetrahydropyran-4-yl                                             13.05                                                                              Ethyl                                                                              (RS)-2H-Tetrahydrothiopy-                                                     ran-3-yl                                                            13.06                                                                              Ethyl                                                                              (R)-2H-Tetrahydrothiopy-                                                      ran-3-yl                                                            13.07                                                                              Ethyl                                                                              (S)-2H-Tetrahydrothiopy-                                                      ran-3-yl                                                            13.08                                                                              Propyl                                                                             (RS)-2H-Tetrahydropyran-3-yl                                        13.09                                                                              Propyl                                                                             (R)-2H-Tetrahydropyran-3-yl                                         13.10                                                                              Propyl                                                                             (S)-2H-Tetrahydropyran-3-yl                                         13.11                                                                              Propyl                                                                             2H-Tetrahydropyran-4-yl                                             13.12                                                                              Propyl                                                                             (RS)-2H-Tetrahydrothiopy-                                                     ran-3-yl                                                            13.13                                                                              Propyl                                                                             (R)-2H-Tetrahydrothiopy-                                                      ran-3-yl                                                            13.14                                                                              Propyl                                                                             (S)-2H-Tetrahydrothiopy-                                                      ran-3-yl                                                            13.15                                                                              Ethyl                                                                              Phenyl                                                              13.16                                                                              Ethyl                                                                              2,4,6-Trimethylphenyl                                               13.17                                                                              Ethyl                                                                              4-(Prop-2-ynyloxy)phenyl                                            13.18                                                                              Propyl                                                                             4-Fluoro-3-nitrophenyl                                              13.19                                                                              Propyl                                                                             (RS)-2-(Ethylthio)prop-1-yl                                         13.20                                                                              Ethyl                                                                              1-Methylthiocycloprop-1-yl                                          13.21                                                                              Ethyl                                                                              1,3-Dimethylpyrazol-5-yl                                            13.22                                                                              Propyl                                                                             3-Isopropylisoxazol-5-yl                                            13.23                                                                              Propyl                                                                             (RS)-Cyclohex-3-en-1-yl                                             __________________________________________________________________________     (*.sup.) predominantly R configuration)                                  

                                      TABLE 14                                    __________________________________________________________________________     ##STR32##                                 I                                                              Phys. data (Rotational                                                        value [α].sub.D .sup.25 ;                   No.  R.sup.1                                                                            R.sup.2           .sup.1 H-NMR [ppm]                                __________________________________________________________________________    14.01                                                                              Ethyl                                                                              (RS)-2H-Tetrahydropyran-3-yl                                        14.02                                                                              Ethyl                                                                              (R)-2H-Tetrahydropyran-3-yl                                         14.03                                                                              Ethyl                                                                              (S)-2H-Tetrahydropyran-3-yl                                         14.04                                                                              Ethyl                                                                              2H-Tetrahydropyran-4-yl                                             14.05                                                                              Ethyl                                                                              (RS)-2H-Tetrahydrothiopy-                                                     ran-3-yl                                                            14.06                                                                              Ethyl                                                                              (R)-2H-Tetrahydrothiopy-                                                      ran-3-yl                                                            14.07                                                                              Ethyl                                                                              (S)-2H-Tetrahydrothiopy-                                                      ran-3-yl                                                            14.08                                                                              Propyl                                                                             (RS)-2H-Tetrahydropyran-3-yl                                        14.09                                                                              Propyl                                                                             (R)-2H-Tetrahydropyran-3-yl                                         14.10                                                                              Propyl                                                                             (S)-2H-Tetrahydropyran-3-yl                                         14.11                                                                              Propyl                                                                             2H-Tetrahydropyran-4-yl                                             14.12                                                                              Propyl                                                                             (RS)-2H-Tetrahydrothiopy-                                                     ran-3-yl                                                            14.13                                                                              Propyl                                                                             (R)-2H-Tetrahydrothiopy-                                                      ran-3-yl                                                            14.14                                                                              Propyl                                                                             (S)-2H-Tetrahydrothiopy-                                                      ran-3-yl                                                            14.15                                                                              Ethyl                                                                              Phenyl                                                              14.16                                                                              Ethyl                                                                              2,4,6-Trimethylphenyl                                               14.17                                                                              Ethyl                                                                              4-(Prop-2-ynyloxy)pheny                                             14.18                                                                              Propyl                                                                             4-Fluoro-3-nitrophenyl                                              14.19                                                                              Propyl                                                                             (RS)-2-(Ethylthio)prop-1-yl                                         14.20                                                                              Ethyl                                                                              1-Methylthiocycloprop-1-yl                                          14.21                                                                              Ethyl                                                                              1,3-Dimethylpyrazol-5-yl                                            14.22                                                                              Propyl                                                                             3-Isopropylisoxazol-5-yl                                            14.23                                                                              Propyl                                                                             (RS)-Cyclohex-3-en-1-yl                                             __________________________________________________________________________     (*.sup.) Racemate: RS configuration)                                     

                                      TABLE 15                                    __________________________________________________________________________     ##STR33##                                 I                                                              Phys. data (Rotational                                                        value [α].sub.D .sup.25 ;                   No.  R.sup.1                                                                            R.sup.2           .sup.1 H-NMR [ppm]                                __________________________________________________________________________    15.01                                                                              Ethyl                                                                              (RS)-2H-Tetrahydropyran-3-yl                                        15.02                                                                              Ethyl                                                                              (R)-2H-Tetrahydropyran-3-yl                                         15.03                                                                              Ethyl                                                                              (S)-2H-Tetrahydropyran-3-yl                                         15.04                                                                              Ethyl                                                                              2H-Tetrahydropyran-4-yl                                             15.05                                                                              Ethyl                                                                              (RS)-2H-Tetrahydrothiopy-                                                     ran-3-yl                                                            15.06                                                                              Ethyl                                                                              (R)-2H-Tetrahydrothiopy-                                                      ran-3-yl                                                            15.07                                                                              Ethyl                                                                              (S)-2H-Tetrahydrothiopy-                                                      ran-3-yl                                                            15.08                                                                              Propyl                                                                             (RS)-2H-Tetrahydropyran-3-yl                                        15.09                                                                              Propyl                                                                             (R)-2H-Tetrahydropyran-3-yl                                         15.10                                                                              Propyl                                                                             (S)-2H-Tetrahydropyran-3-yl                                         15.11                                                                              Propyl                                                                             2H-Tetrahydropyran-4-yl                                             15.12                                                                              Propyl                                                                             (RS)-2H-Tetrahydrothiopy-                                                     ran-3-yl                                                            15.13                                                                              Propyl                                                                             (R)-2H-Tetrahydrothiopy-                                                      ran-3-yl                                                            15.14                                                                              Propyl                                                                             (S)-2H-Tetrahydrothiopy-                                                      ran-3-yl                                                            15.15                                                                              Ethyl                                                                              Phenyl                                                              15.16                                                                              Ethyl                                                                              2,4,6-Trimethylphenyl                                               15.17                                                                              Ethyl                                                                              4-(Prop-2-ynyloxy)phenyl                                            15.18                                                                              Propyl                                                                             4-Fluoro-3-nitrophenyl                                              15.19                                                                              Propyl                                                                             (RS)-2-(Ethylthio)prop-1-yl                                         15.20                                                                              Ethyl                                                                              1-Methylthiocycloprop-1-yl                                          15.21                                                                              Ethyl                                                                              1,3-Dimethylpyrazol-5-yl                                            15.22                                                                              Propyl                                                                             3-Isopropylisoxazol-5-yl                                            15.23                                                                              Propyl                                                                             (RS)-Cyclohex-3-en-1-yl                                             __________________________________________________________________________     (*.sup.) predominantly R configuration)                                  

                                      TABLE 16                                    __________________________________________________________________________     ##STR34##                                 I                                                              Phys. data (Rotational                                                        value [α].sub.D .sup.25 ;                   No.  R.sup.1                                                                            R.sup.2           .sup.1 H-NMR [ppm]                                __________________________________________________________________________    16.01                                                                              Ethyl                                                                              (RS)-2H-Tetrahydropyran-3-yl                                        16.02                                                                              Ethyl                                                                              (R)-2H-Tetrahydropyran-3-yl                                         16.03                                                                              Ethyl                                                                              (S)-2H-Tetrahydropyran-3-yl                                         16.04                                                                              Ethyl                                                                              2H-Tetrahydropyran-4-yl                                             16.05                                                                              Ethyl                                                                              (RS)-2H-Tetrahydrothiopy-                                                     ran-3-yl                                                            16.06                                                                              Ethyl                                                                              (R)-2H-Tetrahydrothiopy-                                                      ran-3-yl                                                            16.07                                                                              Ethyl                                                                              (S)-2H-Tetrahydrothiopy-                                                      ran-3-yl                                                            16.08                                                                              Propyl                                                                             (RS)-2H-Tetrahydropyran-3-yl                                        16.09                                                                              Propyl                                                                             (R)-2H-Tetrahydropyran-3-yl                                         16.10                                                                              Propyl                                                                             (S)-2H-Tetrahydropyran-3-yl                                         16.11                                                                              Propyl                                                                             2H-Tetrahydropyran-4-yl                                             16.12                                                                              Propyl                                                                             (RS)-2H-Tetrahydrothiopy-                                                     ran-3-yl                                                            16.13                                                                              Propyl                                                                             (R)-2H-Tetrahydrothiopy-                                                      ran-3-yl                                                            16.14                                                                              Propyl                                                                             (S)-2H-Tetrahydrothiopy-                                                      ran-3-yl                                                            16.15                                                                              Ethyl                                                                              Phenyl                                                              16.16                                                                              Ethyl                                                                              2,4,6-Trimethylphenyl                                               16.17                                                                              Ethyl                                                                              4-(Prop-2-ynyloxy)phenyl                                            16.18                                                                              Propyl                                                                             4-Fluoro-3-nitrophenyl                                              16.19                                                                              Propyl                                                                             (RS)-2-(Ethylthio)prop-1-yl                                         16.20                                                                              Ethyl                                                                              1-Methylthiocycloprop-1-yl                                          16.21                                                                              Ethyl                                                                              1,3-Dimethylpyrazol-5-yl                                            16.22                                                                              Propyl                                                                             3-Isopropylisoxazol-5-yl                                            16.23                                                                              Propyl                                                                             (RS)-Cyclohex-3-en-1-yl                                             __________________________________________________________________________     (*.sup.) Racemate; RS configuration)                                     

                                      TABLE 17                                    __________________________________________________________________________     ##STR35##                                 I                                                              Phys. data (Rotational                                                        value [α].sub.D .sup.25 ;                   No.  R.sup.1                                                                            R.sup.2           .sup.1 H-NMR [ppm]                                __________________________________________________________________________    17.01                                                                              Ethyl                                                                              (RS)-2H-Tetrahydropyran-3-yl                                        17.02                                                                              Ethyl                                                                              (R)-2H-Tetrahydropyran-3-yl                                         17.03                                                                              Ethyl                                                                              (S)-2H-Tetrahydropyran-3-yl                                         17.04                                                                              Ethyl                                                                              2H-Tetrahydropyran-4-yl                                             17.05                                                                              Ethyl                                                                              (RS)-2H-Tetrahydrothiopy-                                                     ran-3-yl                                                            17.06                                                                              Ethyl                                                                              (R)-2H-Tetrahydrothiopy-                                                      ran-3-yl                                                            17.07                                                                              Ethyl                                                                              (S)-2H-Tetrahydrothiopy-                                                      ran-3-yl                                                            17.08                                                                              Propyl                                                                             (RS)-2H-Tetrahydropyran-3-yl                                        17.09                                                                              Propyl                                                                             (R)-2H-Tetrahydropyran-3-yl                                         17.10                                                                              Propyl                                                                             (S)-2H-Tetrahydropyran-3-yl                                         17.11                                                                              Propyl                                                                             2H-Tetrahydropyran-4-yl                                             17.12                                                                              Propyl                                                                             (RS)-2H-Tetrahydrothiopy-                                                     ran-3-yl                                                            17.13                                                                              Propyl                                                                             (R)-2H-Tetrahydrothiopy-                                                      ran-3-yl                                                            17.14                                                                              Propyl                                                                             (S)-2H-Tetrahydrothiopy-                                                      ran-3-yl                                                            17.15                                                                              Ethyl                                                                              Phenyl                                                              17.16                                                                              Ethyl                                                                              2,4,6-Trimethylphenyl                                               17.17                                                                              Ethyl                                                                              4-(Prop-2-ynyloxy)phenyl                                            17.18                                                                              Propyl                                                                             4-Fluoro-3-nitrophenyl                                              17.19                                                                              Propyl                                                                             (RS)-2-(Ethylthio)prop-1-yl                                         17.20                                                                              Ethyl                                                                              1-Methylthiocycloprop-1-yl                                          17.21                                                                              Ethyl                                                                              1,3-Dimethylpyrazol-5-yl                                            17.22                                                                              Propyl                                                                             3-Isopropylisoxazol-5-yl                                            17.23                                                                              Propyl                                                                             (RS)-Cyclohex-3-en-1-yl                                             __________________________________________________________________________     (*.sup.) predominantly R configuration)                                  

The optically active cyclohexenone oxime ethers I are suitable, both asisomer mixtures and in the form of the pure isomers, as herbicidesespecially for combating plants from the Gramineae species. They aregenerally well tolerated and are thus selective in broadleaved crops andin monocotyledons not belonging to the Gramineae. Some of thecyclohexenone oxime ethers I according to the invention are alsosuitable for selectively combating unwanted grasses in Gramineae.

The optically active cyclohexenone oxime ethers I, or herbicidal agentscontaining them, may be applied for instance in the form of directlysprayable solutions, powders, suspensions (including high-percentageaqueous, oily or other suspensions), dispersions, emulsions, oildispersions, pastes, dusts, broadcasting agents, or granules byspraying, atomizing, dusting, broadcasting or watering. The forms ofapplication depend entirely on the purpose for which the agents arebeing used, but they should ensure as fine a distribution of the activeingredients according to the invention as possible.

The compositions I are generally suitable for the preparation ofsolutions, emulsions, pastes and oil dispersions to be sprayed direct.Examples of suitable inert additives are mineral oil fractions of mediumto high boiling point, such as kerosene or diesel oil, further coal-taroils, and oils of vegetable or animal origin, aliphatic, cyclic andaromatic hydrocarbons such as toluene, xylene, paraffin,tetrahydronaphthalene, alkylated naphthalenes and their derivatives,methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone,chlorobenzene, isophorone, etc., and strongly polar solvents such asN,N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, water,etc.

Aqueous formulations may be prepared from emulsion concentrates, pastes,oil dispersions, wettable powders or water-dispersible granules byadding water. To prepare emulsions, pastes and oil dispersions theingredients as such or dissolved in an oil or solvent may be homogenizedin water by means of wetting or dispersing agents, adherents oremulsifiers. Concentrates which are suitable for dilution with water maybe prepared from active ingredient, wetting agent, adherent, emulsifyingor dispersing agent and possibly solvent or oil.

Examples of surfactants are: alkali metal, alkaline earth metal andammonium salts of aromatic sulfonic acids, e.g., ligninsulfonic acid,phenolsulfonic acid, naphthalenesulfonic acid anddibutylnaphthalenesulfonic acid, and of fatty acids, alkyl and alkylarylsulfonates, and alkyl, lauryl ether and fatty alcohol sulfates, andsalts of sulfated hexadecanols, heptadecanols, and octadecanols, saltsof fatty alcohol glycol ethers, condensation products of sulfonatednaphthalene and naphthalene derivatives with formaldehyde, condensationproducts of naphthalene or naphthalenesulfonic acids with phenol andformaldehyde, polyoxyethylene octylphenol ethers, ethoxylatedisooctylphenol, ethoxylated octylphenol and ethoxylated nonylphenol,alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers,alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcoholethylene oxide condensates, ethoxylated castor oil, polyoxyethylenealkyl ethers, ethoxylated polyoxylpropylene, lauryl alcohol polyglycolether acetal, sorbitol esters, lignin-sulfite waste liquors and methylcellulose.

Powders, dusts and broadcasting agents may be prepared by mixing orgrinding the active ingredients with a solid carrier.

Granules, e.g., coated, impregnated or homogeneous granules, may beprepared by bonding the active ingredients to solid carriers. Examplesof solid carriers are mineral earths such as silicic acids, silica gels,silicates, talc, kaolin, attapulgus clay, limestone, lime, chalk, bole,loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesiumsulfate, magnesium oxide, ground plastics, fertilizers such as ammoniumsulfate, ammonium phosphate, ammonium nitrate, and ureas, and vegetableproducts such as grain meals, bark meal, wood meal, and nutshell meal,cellulosic powders, etc.

The formulations contain from 0.01 to 95, and preferably 0.5 to 90%, byweight of active ingredient. The active ingredients are used in a purityof 90 to 100, and preferably 95 to 100%, (according to the NMRspectrum).

Examples of formulations are as follows:

I. A solution of 90 parts by weight of compound no. 2.01 and 10 parts byweight of N-methyl-α-pyrrolidone, which is suitable for application inthe form of very fine drops.

II. A mixture of 20 parts by weight of compound no. 2.03, 80 parts byweight of xylene, 10 parts by weight of the adduct of 8 to 10 moles ofethylene oxide and 1 mole of oleic acid-N-monoethanolamide, 5 parts byweight of the calcium salt of dodecylbenzenesulfonic acid, and 5 partsby weight of the adduct of 40 moles of ethylene oxide and 1 mole ofcastor oil. By finely dispersing the mixture in 100,000 parts by weightof water, an aqueous dispersion containing 0.02 wt % of the activeingredient is obtained.

III. An aqueous dispersion of 20 parts by weight of compound no. 2.05,40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol,20 parts by weight of the adduct of 40 moles of ethylene oxide and 1mole of castor oil. A mixture of this dispersion with 100,000 parts byweight of water contains 0.02 wt % of the active ingredient.

IV. An aqueous dispersion of 20 parts by weight of compound no. 2.07, 25parts by weight of cyclohexanone, 65 parts by weight of a mineral oilfraction having a boiling point of from 210° to 280° C., and 10 parts byweight of the adduct of 40 moles of ethylene oxide and 1 mole of castoroil. The mixture of this dispersion with 100,000 parts by weight ofwater contains 0.02 wt % of the active ingredient.

V. A hammer-milled mixture of 80 parts by weight of compound no. 2.09, 3parts by weight of the sodium salt of diisobutylnaphthalene-α-sulfonicacid, 10 parts by weight of the sodium salt of a lignin-sulfonic acidobtained from a sulfite waste liquor, and 7 parts by weight of powderedsilica gel. By finely dispersing the mixture in 20,000 parts by weightof water, a spray liquor containing 0.1 wt % of the active ingredient isobtained.

VI. An intimate mixture of 3 parts by weight of compound no. 2.11 and 97parts by weight of particulate kaolin. The dust contains 3 wt % of theactive ingredient.

VII. An intimate mixture of 30 parts by weight of compound no. 2.13, 92parts by weight of powdered silica gel and 8 parts by weight of paraffinoil sprayed onto the surface of this silica gel. This formulation of theactive ingredient exhibits good adherence.

VIII. A stable aqueous dispersion of 40 parts by weight of compound no.2.15, 10 parts of the sodium salt of a phenolsulfonicacid-urea-formaldehyde condensate, 2 parts of silica gel and 48 parts ofwater, which dispersion can be further diluted.

IX. A stable oily dispersion of 20 parts by weight of compound no. 3.01,2 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, 8parts by weight of a fatty alcohol polyglycol ether, 20 parts by weightof the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensateand 68 parts by weight of a paraffinic mineral oil.

X. A hammer-milled mixture of 10 parts by weight of compound no. 4.03, 4parts by weight of the sodium salt of diisobutylnaphthalene-α-sulfonicacid, 20 parts by weight of the sodium salt of a lignin-sulfonic acidobtained from a sulfite waste liquor, and 38 parts by weight of silicagel and 38 parts by weight of kaolin. By finely dispersing the mixturein 10,000 parts by weight of water, a spray liquor containing 0.1 wt %of the active ingredient is obtained.

The active ingredients or the herbicidal agents containing them may beapplied pre- or postemergence. If certain crop plants tolerate theactive ingredients less well, application techniques may be used inwhich the herbicidal agents are sprayed from suitable equipment in sucha manner that the leaves of sensitive crop plants are if possible nottouched, and the agents reach the uncovered soil or the leaves ofunwanted plants growing beneath the crop plants (post-directed, lay-bytreatment).

The application rates depend on the objective to be achieved, the timeof the year, the plants to be combated and their growth stage, and arefrom 0.001 to 3, preferably 0.01 to 1, kg of active ingredient perhectare.

In view of the numerous application methods possible, the cyclohexenoneoxime ethers I or the agents containing them may also be used in afurther number of crops for eliminating unwanted plants. Those whichfollow are given by way of example:

    ______________________________________                                        Allium cepa          onions                                                   Ananas comosus       pineapples                                               Arachis hypogaea     peanuts (groundnuts)                                     Asparagus officinalis                                                                              asparagus                                                Beta vuigaris spp. altissima                                                                       sugarbeets                                               Beta vuigaris spp. rapa                                                                            fodder beets                                             Brassica napus var. napus                                                                          rapeseed                                                 Brassica napus var. napobrassica                                                                   swedes                                                   Brassica rapa var. silvestris                                                 Camellia sinensis    tea plants                                               Carthamus tinctorius safflower                                                Carya illinoinensis  pecan trees                                              Citrus limon         lemons                                                   citrus sinensis      orange trees                                             Coffea arabica (Coffea canephora,                                                                  coffee plants                                            Coffea liberica)                                                              Cucumis sativus      cucumbers                                                Cynodon dactylon     Bermudagrass                                             Daucus carota        carrots                                                  Elais guineensis     oil palm                                                 Fragaria vesca       strawberries                                             Glycine max          soybeans                                                 Gossypium hirsutum (Gossypium                                                                      cotton                                                   arboreum,                                                                     Gossypium herbaceum,                                                          Gossypium vitifolium)                                                         Helianthus annuus    sunflowers                                               Hevea brasiliensis   rubber plants                                            Hordeum vulgare      barley                                                   Humulus lupulus      hops                                                     Ipomoea batatas      sweet potatoes                                           Juglans regia        walnut trees                                             Lens culinaris       lentils                                                  Linum usitatissimum  flax                                                     Lycopersicon lycopersicum                                                                          tomatoes                                                 Malus spp.           apple trees                                              Manihot esculenta    cassava                                                  Medicago sativa      alfalfa (lucerne)                                        Musa spp.            banana plants                                            Nicotiana tabacum (N. rustics)                                                                     tobacco                                                  Olea europaea        olive trees                                              Oryza sativa         rice                                                     Phaseolus lunatus    limabeans                                                Phaseolus vulgaris   snapbeans, green be-                                                          ans, dry beans                                           Picea abies          Norway spruce                                            Pinus spp.           pine trees                                               Pisum sativum        English peas                                             Prunus avium         cherry trees                                             Prunus persica       peach trees                                              Pyrus communis       pear trees                                               Ribes sylvestre      redcurrants                                              Ricinus communis     castor-oil plants                                        Saccharum officinarum                                                                              sugar cane                                               Secale cereale       rye                                                      Solanum tuberosum    Irish potatoes                                           Sorghum bicolor (s. vulgare)                                                                       sorghum                                                  Theobroma cacao      cacao plants                                             Trifolium pratense   red clover                                               Triticum aestivum    wheat                                                    Triticum durum       wheat                                                    Vicia faba           tick beans                                               Vitis vinitera       grapes                                                   Zea mays             Indian corn, sweet                                                            corn, maize                                              ______________________________________                                    

To increase the spectrum of action and to achieve synergistic effects,the cyclohexenone oxime ethers I may be mixed and applied together withnumerous representatives of other herbicidal or growth-regulating activeingredient groups. Examples of suitable components are diazines,4H-3,1-benzoxazine derivatives, benzothiadiazinones,2,6-dinitroanilines, N-phenylcarbamates, thiolcarbamates, halocarboxylicacids, triazines, amides, ureas, diphenyl ethers, triazinones, uracils,benzofuran derivatives, cyclohexane-1,3-dione derivatives bearing in the2-position for example a carboxy or carbimino group, quinolinecarboxylicacids, imidazolinones, sulfonamides, sulfonylureas,(hetero)-aryloxyphenoxypropionic acids and salts, esters, amidesthereof, etc.

It may also be useful to apply the compounds I, either alone or incombination with other herbicides, in admixture with other cropprotection agents, e.g., agents for combating pests or phytopathogenicfungi or bacteria. Further interest attaches to the miscibility withsolutions of mineral salts used to remedy nutritional or trace elementdeficiencies. Non-phytotoxic oils and oil concentrates may also beadded.

USE EXAMPLES

The herbicidal action of the unsaturated cyclohexenone oxime ethers ofthe formula I is demonstrated in greenhouse experiments:

The vessels employed were plastic flowerpots filled with a sandy loamcontaining about 3.0% humus. The seeds of the test plants were sownseparately, according to species.

For the preemergence treatment, the active ingredients, emulsified orsuspended in water were applied immediately after the seeds had beensown, and sprayed through finely distributing nozzles. The vessels werelightly sprinkler-irrigated to induce germination and growth.Transparent plastic covers were then placed on the vessels until theplants had taken root. The cover ensured uniform germination of theplants, insofar as this was not impaired by the active ingredients.

For the postemergence treatment, plants were used which had been sown inthe pots and grown there, or they were grown separately as seedlings andtransplanted to the pots a few days before treatment. The plants weregrown, depending on growth form, to a height of 3 to 15 cm before beingtreated with the compounds, suspended or emulsified in water. Theapplication rate for postemergence treatment was 0.25 kg/ha.

The pots were set up, at temperatures specific to their species, of 20°to 35° C., or 10° to 25° C. The experiments were run for from 2 to 4weeks. During this period the plants were tended and their reactions tothe various treatments assessed.

The assessment scale was 0 to 100,100 denoting nonemergence or completedestruction of at least the visible plant parts, and 0 denoting nodamage or normal growth.

We claim:
 1. Mixtures of optically active cyclohexenone oxime ethers,having R- and S-configuration in the oxime ether moiety and containingat least 50 mol % of the R-configuration, of the formula I ##STR36##where: R¹ is C₁ -C₆ -alkylZ is one of the following groups: ##STR37## Xis halogen or C₁ -C₄ -haloalkyl; m is from 0 to 3, or from 1 to 4 whereall X's are halogen; n is from 0 to 3, or from 1 to 5 where all X's arehalogen; R² is C₁ -C₄ -alkoxy-C₁ -C₆ -alkyl or C₁ -C₄ -alkylthio-C₁ -C₆-alkyl; C₃ -C₇ -cycloalkyl or C₅ -C₇ -cycloalkenyl, where these groupsare unsubstituted or bear from one to three substituents selected fromthe group consisting of C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, C₁ -C₄-alkylthio, C₁ -C₄ -haloalkyl, hydroxyl and halogen; the 5-memberedheterocyclic structure tetrahydrofuranyl tetrahydrothienyl ordioxolanyl, which heterocyclic structure is unsubstituted or bears fromone to three substituents selected from the group consisting of C₁ -C₄-alkyl, C₁ -C₄ -alkoxy, C₁ -C₄ -alkylthio and C₁ -C₄ -haloalkyl; a 6- or7-membered saturated or mono- or diunsaturated heterocyclic structurewhich in addition to the carbon atoms of the ring has one or two oxygenor sulfur atoms or one oxygen and one sulfur atom as heteroatoms andwhich is unsubstituted or bears from one to three substituents selectedfrom the group consisting of hydroxyl, halogen, C₁ -C₄ -alkyl, C₁ -C₄-alkoxy, C₁ -C₄ -alkylthio and C₁ -C₄ -haloalkyl; a 5-memberedheteroaromatic structure selected from the group consisting ofisoxazolyl and furanyl, which heteroaromatic structure is unsubstitutedor bears from one to three substituents selected from the groupconsisting of halogen, cyano, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, C₁ -C₄-alkylthio, C₁ -C₄ -haloalkyl, C₂ -C₆ -alkenyl, C₂ -C₆ -alkenyloxy andC₁ -C₄ -alkoxy-C₁ -C₄ -alkyl; phenyl or pyridyl, where these aromaticstructures are unsubstituted or bear from one to three substituentsselected from the group consisting of nitro, C₁ -C₄ -alkyl, and C₃ -C₆-alkynyloxyor the agriculturally useful salts and esters of thecompounds I with C₁ -C₁₀ -carboxylic acids.
 2. Optically activecyclohexenone oxime ethers I as set forth in claim 1 having from 90 to100 mol % of the R-configuration in the oxime ether moiety.
 3. Mixturesof optically active cyclohexenone oxime ethers as defined in claim 1,wherein in formula I, Z is phenyl, X is halogen and n is 0 to
 3. 4.Mixtures of optically active cyclohexenone oxime ethers of the formulaI, as defined in claim 1, wherein R¹ is ethyl, R² is2H-tetrahydropyran-4-yl and Z is 2,4-dichlorophenyl.
 5. A herbicidalcomposition containing inert additives and a herbicidally effectiveamount of a mixture of optically active cyclohexenone oxime ethers ofthe formula I as set forth in claim
 1. 6. A method of combating thegrowth of unwanted plants, wherein a herbicidally effective amount of amixture of optically active cyclohexenone oxime ethers I as set forth inclaim 1 is allowed to act on the plants, their habitat or their seed.